JP7079204B2 - Copolymer rubber and its production method, and crosslinked rubber composition - Google Patents
Copolymer rubber and its production method, and crosslinked rubber composition Download PDFInfo
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- JP7079204B2 JP7079204B2 JP2018549003A JP2018549003A JP7079204B2 JP 7079204 B2 JP7079204 B2 JP 7079204B2 JP 2018549003 A JP2018549003 A JP 2018549003A JP 2018549003 A JP2018549003 A JP 2018549003A JP 7079204 B2 JP7079204 B2 JP 7079204B2
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- copolymer
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- 229920001971 elastomer Polymers 0.000 title claims description 129
- 239000005060 rubber Substances 0.000 title claims description 128
- 229920001577 copolymer Polymers 0.000 title claims description 122
- 239000000203 mixture Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- -1 diene compound Chemical class 0.000 claims description 93
- 229920002554 vinyl polymer Polymers 0.000 claims description 77
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 20
- 150000001491 aromatic compounds Chemical class 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 14
- 239000012986 chain transfer agent Substances 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
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- 230000015572 biosynthetic process Effects 0.000 description 12
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- 230000003993 interaction Effects 0.000 description 12
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
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- 238000003786 synthesis reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
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- 125000000524 functional group Chemical group 0.000 description 6
- 229920003049 isoprene rubber Polymers 0.000 description 6
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 4
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 238000004817 gas chromatography Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 3
- HPUCAWBFVXHLDN-UHFFFAOYSA-N 1-but-1-enyl-2-phenylbenzene Chemical group CCC=CC1=CC=CC=C1C1=CC=CC=C1 HPUCAWBFVXHLDN-UHFFFAOYSA-N 0.000 description 3
- AKRICVNYDOTXCL-UHFFFAOYSA-N 1-but-1-enylnaphthalene Chemical compound C1=CC=C2C(C=CCC)=CC=CC2=C1 AKRICVNYDOTXCL-UHFFFAOYSA-N 0.000 description 3
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
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- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
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- WCBXINYQNFNCSF-UHFFFAOYSA-N 1-phenyl-2-prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1C1=CC=CC=C1 WCBXINYQNFNCSF-UHFFFAOYSA-N 0.000 description 2
- ZZPDMMIMRUGHBQ-UHFFFAOYSA-N 1-prop-1-enylnaphthalene Chemical compound C1=CC=C2C(C=CC)=CC=CC2=C1 ZZPDMMIMRUGHBQ-UHFFFAOYSA-N 0.000 description 2
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- TXQHJLUVWZNSLH-UHFFFAOYSA-N 5-ethenyl-2,5-dimethylcyclohexa-1,3-diene Chemical compound CC1(C=C)CC=C(C=C1)C TXQHJLUVWZNSLH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- BTQLDZMOTPTCGG-UHFFFAOYSA-N cyclopentyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCC1 BTQLDZMOTPTCGG-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- XBCUZBAUBAMRPO-UHFFFAOYSA-N dimethyl(2-phenylethenyl)silane Chemical compound C[SiH](C)C=CC1=CC=CC=C1 XBCUZBAUBAMRPO-UHFFFAOYSA-N 0.000 description 1
- AOMLTDAXFAUSNN-UHFFFAOYSA-N dimethyl-(2-phenyl-1-propan-2-yloxyethenyl)silane Chemical compound C(C)(C)OC(=CC1=CC=CC=C1)[SiH](C)C AOMLTDAXFAUSNN-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- DSNYFFJTZPIKFZ-UHFFFAOYSA-N propoxybenzene Chemical compound CCCOC1=CC=CC=C1 DSNYFFJTZPIKFZ-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/044—Polymers of aromatic monomers as defined in group C08F12/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、加工性に優れ、かつ、引張強度と耐摩耗性に優れる共重合体ゴム及びそれを架橋した架橋ゴム生成物に関する。 The present invention relates to a copolymer rubber having excellent processability and excellent tensile strength and wear resistance, and a crosslinked rubber product obtained by cross-linking the copolymer rubber.
SBR(スチレン-ブタジエンゴム)、BR(ブタジエンゴム)、IR(イソプレンゴム)スチレン-イソプレンゴム、等の共役ジエンゴムは、耐摩耗性、弾性、耐水性に優れ、成型材料、樹脂の改質剤等の様々な用途に用いられている。 Conjugate diene rubbers such as SBR (styrene-butadiene rubber), BR (butadiene rubber), IR (isoprene rubber) styrene-isoprene rubber, etc. have excellent wear resistance, elasticity, water resistance, molding materials, resin modifiers, etc. It is used for various purposes.
この共役ジエンゴムの主要な用途の一つとして、自動車用のタイヤが挙げられる。タイヤにおいて要求される特性としては、機械的強度、耐摩耗性、ウェットグリップ性等(以下、併せて、強度等ともいう。)が挙げられる。さらに近年では、省エネ性能、つまり低燃費性に優れるタイヤ(いわゆる「エコタイヤ」)の開発が活発に行われてきている。このエコタイヤは、強度に加え、転がり抵抗が小さいことが要求される。 One of the main uses of this conjugated diene rubber is an automobile tire. The characteristics required for a tire include mechanical strength, wear resistance, wet grip property and the like (hereinafter, also referred to as strength and the like). Further, in recent years, tires having excellent energy-saving performance, that is, fuel efficiency (so-called "eco-tires") have been actively developed. This eco-tire is required to have low rolling resistance in addition to strength.
タイヤの強度等を担保するために、共役ジエンゴムにカーボンブラックやシリカ等のフィラー(補強用充填剤)を添加することが知られているが、タイヤの強度をさらに向上させるとともに、優れた転がり抵抗を付与する材料として、末端変性溶液重合型SBR(末端変性S-SBR)が注目されている。末端変性S-SBRは、SBRの分子末端に官能基を有し、この分子末端の官能基がフィラーと相互作用する。この相互作用により、SBR中のフィラーの分散性が向上するとともに、SBRの分子末端が拘束されて運動性が低下する。その結果、タイヤのヒステリシスロス(内部摩擦)が低減し、転がり抵抗が低下する。この特性を活かし、強度と低転がり抵抗を兼ね備えたエコタイヤの開発が行われている。 It is known to add a filler (reinforcing filler) such as carbon black or silica to conjugated diene rubber in order to secure the strength of the tire, but the strength of the tire is further improved and the excellent rolling resistance is obtained. As a material for imparting a tire, end-modified solution-polymerized SBR (terminal-modified S-SBR) is attracting attention. The terminal-modified S-SBR has a functional group at the molecular end of SBR, and the functional group at the molecular end interacts with the filler. This interaction improves the dispersibility of the filler in the SBR and constrains the molecular ends of the SBR to reduce motility. As a result, the hysteresis loss (internal friction) of the tire is reduced, and the rolling resistance is reduced. Taking advantage of this characteristic, eco-tires that have both strength and low rolling resistance are being developed.
例えば、特許文献1では、非極性溶媒中で有機リチウム化合物を開始剤として用い、リビングアニオン重合により、α-メチルスチレンブロックとブタジエンブロックからなるブロック共重合体を合成し、さらに必要により多官能性カップリング剤を反応させることで、高温特性とゴム的性質を兼ね備えたS-SBRを得ている。
また、特許文献2では、共役ジエン及びモノビニル芳香族モノマーのランダムコポリマーブロックと、ポリ共役ジエンブロックと、多官能性リチウム系開始剤由来の官能基とを有する、星形-ブロックインターポリマーが開示され、転がり抵抗の低減やトラクション特性の改善といった優れた特性を有するタイヤトレッドの作製におけるゴムとして、広く使用することができることが開示されている。
特許文献1及び2の技術は、ゴム成分に分岐構造を導入することで、ゴムの加工性を担保する効果があると考えられる。しかし、強度を担保するためのフィラーとの相互作用については、特段の工夫はなく、強度に対する寄与は十分ではない。For example, in Patent Document 1, an organic lithium compound is used as an initiator in a non-polar solvent, and a block copolymer composed of α-methylstyrene block and butadiene block is synthesized by living anionic polymerization, and further, if necessary, polyfunctionality. By reacting the coupling agent, S-SBR having both high temperature characteristics and rubber-like properties is obtained.
Further, Patent Document 2 discloses a star-block interpolymer having a random copolymer block of conjugated diene and a monovinyl aromatic monomer, a polyconjugated diene block, and a functional group derived from a polyfunctional lithium-based initiator. It is disclosed that it can be widely used as a rubber in the production of a tire tread having excellent properties such as reduction of rolling resistance and improvement of traction characteristics.
The techniques of Patent Documents 1 and 2 are considered to have an effect of ensuring the workability of rubber by introducing a branched structure into the rubber component. However, there is no particular device for the interaction with the filler to ensure the strength, and the contribution to the strength is not sufficient.
また、特許文献3では、複数のジエン系ゴムを含むブレンドゴムに、所定量のカーボンブラックを配合したゴム組成物に、分子鎖末端に前記カーボンブラックと相互作用のある官能基を有し、かつ前記ジエン系ゴムのゴム成分に類似するポリマー構造からなる低分子量の官能基含有ポリマーを配合してなるゴム組成物が開示されている。このゴム組成物は、カーボンブラックと相互作用を有する低分子化合物をゴムへ配合することにより、各ジエン系ゴム成分中へのカーボンブラック分配量を制御できる。そのため、各々のゴム成分の特長を有効に発現させ、例えば転がり特性とウェット特性のような背反関係にあるゴム特性の両立を図ることができる。しかし、この技術は、低分子量化合物をゴムに対して配合するため、強度に対する寄与としては十分ではない。
また、特許文献4では、共役ジエン単量体単位、芳香族ビニル単量体単位及び少なくとも2個の重合性不飽和基を有する単量体単位を含む架橋ゴム粒子、並びに、特定の結合構造を有する共役ジエン単量体単位を含む共役ジエン/芳香族ビニル共重合ゴムを含有するゴム組成物が開示され、この架橋ゴム粒子はカルボン酸基、ヒドロキシル基及び/又はエポキシ基を有する単量体単位を含んでも良いと開示されている。この技術は、シリカ等の無機充填剤(フィラー)との適度な相互作用を有することから、無機充填剤の分散性や加工性に優れる。しかし、前記少なくとも2個の重合性不飽和基を有する単量体単位や、カルボン酸基、ヒドロキシル基及び/又はエポキシ基を有する単量体単位として開示されている物質は、いずれも低分子である。そのため、反応性が過剰に高く、架橋ゴム粒子及びゴム組成物においてゲル化が進行する恐れがあった。また、この技術は共役ジエン/芳香族ビニル共重合ゴムとは別途架橋ゴムを合成した上で、その架橋ゴムを共役ジエン/芳香族ビニル共重合ゴムと配合することが必須であり、工程の簡易性の観点で、改善が必要である。
特許文献5は、可溶性多官能ビニル芳香族共重合体を開示するが、これを共重合体ゴムの製造に使用することは教えない。Further, in Patent Document 3, a rubber composition in which a predetermined amount of carbon black is blended with a blended rubber containing a plurality of diene-based rubbers has a functional group having an interaction with the carbon black at the end of the molecular chain and A rubber composition comprising a low molecular weight functional group-containing polymer having a polymer structure similar to the rubber component of the diene-based rubber is disclosed. In this rubber composition, the amount of carbon black distributed into each diene-based rubber component can be controlled by blending a small molecule compound having an interaction with carbon black into the rubber. Therefore, the characteristics of each rubber component can be effectively expressed, and it is possible to achieve both rolling characteristics and rubber characteristics that have a contradictory relationship such as wet characteristics. However, this technique is not sufficient as a contribution to strength because it blends low molecular weight compounds with rubber.
Further, in Patent Document 4, a crosslinked rubber particle containing a conjugated diene monomer unit, an aromatic vinyl monomer unit and a monomer unit having at least two polymerizable unsaturated groups, and a specific bonded structure are used. A rubber composition containing a conjugated diene / aromatic vinyl copolymerized rubber containing a conjugated diene monomer unit having is disclosed, and the crosslinked rubber particles are monomer units having a carboxylic acid group, a hydroxyl group and / or an epoxy group. It is disclosed that it may include. Since this technique has an appropriate interaction with an inorganic filler (filler) such as silica, the inorganic filler is excellent in dispersibility and processability. However, the substances disclosed as the above-mentioned monomer unit having at least two polymerizable unsaturated groups and the monomer unit having a carboxylic acid group, a hydroxyl group and / or an epoxy group are all small molecules. be. Therefore, the reactivity is excessively high, and there is a risk that gelation will proceed in the crosslinked rubber particles and the rubber composition. In addition, in this technology, it is essential to synthesize a crosslinked rubber separately from the conjugated diene / aromatic vinyl copolymerized rubber and then blend the crosslinked rubber with the conjugated diene / aromatic vinyl copolymerized rubber, which simplifies the process. From a sexual point of view, improvement is needed.
Patent Document 5 discloses a soluble polyfunctional vinyl aromatic copolymer, but does not teach that it is used in the production of copolymer rubber.
本発明は、かかる課題を解決し、加工性、強度及び均質性を兼ね備えた材料を提供することを目的とする。 An object of the present invention is to solve such a problem and to provide a material having workability, strength and homogeneity.
本発明者らは、鋭意検討を重ねた結果、共役ジエンゴムの構成単位として、分岐構造及びフィラーとの相互作用機能を併せ持つ、特定の多官能ビニル芳香族共重合体化合物を用いることで、上記の課題を解決することを見出し、本発明を完成した。 As a result of diligent studies, the present inventors have obtained the above-mentioned by using a specific polyfunctional vinyl aromatic copolymer compound having a branched structure and an interaction function with a filler as a constituent unit of the conjugated diene rubber. The present invention was completed by finding a solution to the problem.
本発明は、多官能ビニル芳香族共重合体(A)、及び共役ジエン化合物(B)を含む原料を共重合させて共重合体ゴムを製造するに当たり、
多官能ビニル芳香族共重合体(A)が、ジビニル芳香族化合物に由来する構造単位(a)、モノビニル芳香族化合物に由来する構造単位(b)、及び末端を構成する構造単位(d)を含有し、構造単位(a)を2モル%以上95モル%未満含有し、構造単位(a)の少なくとも一部は下記式で表されるビニル基含有構造単位(a1)であり、
(式中、R1は炭素数6~30の芳香族炭化水素基を示す。)
構造単位(a)の他の少なくとも一部は上記構造単位(d)を構成する構造単位であり、構造単位(a)及び(b)の総和に対するビニル基含有構造単位(a1)モル分率は0.02~0.8の範囲であり、数平均分子量が300~100000であることを特徴とする共重合体ゴムの製造方法である。In the present invention, in producing a copolymer rubber by copolymerizing a raw material containing a polyfunctional vinyl aromatic copolymer (A) and a conjugated diene compound (B).
The polyfunctional vinyl aromatic copolymer (A) has a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (d) constituting a terminal. It contains 2 mol% or more and less than 95 mol% of the structural unit (a), and at least a part of the structural unit (a) is a vinyl group-containing structural unit (a1) represented by the following formula.
(In the formula, R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.)
At least a part of the other structural unit (a) is a structural unit constituting the structural unit (d), and the molar fraction of the vinyl group-containing structural unit (a1) with respect to the sum of the structural units (a) and (b) is It is a method for producing a copolymer rubber, which is in the range of 0.02 to 0.8 and has a number average molecular weight of 300 to 100,000.
また、本発明は、多官能ビニル芳香族共重合体(A)と、共役ジエン化合物(B)又は共役ジエン化合物(B)と芳香族ビニル化合物(C)を含む原料を共重合させて共重合体ゴムを製造するに当たり、多官能ビニル芳香族共重合体(A)として、上記多官能ビニル芳香族共重合体を使用することを特徴とする共重合体ゴムの製造方法である。 Further, in the present invention, the polyfunctional vinyl aromatic copolymer (A) is copolymerized with a raw material containing a conjugated diene compound (B) or a conjugated diene compound (B) and an aromatic vinyl compound (C) to have a copolymer weight. A method for producing a copolymer rubber, which comprises using the above-mentioned polyfunctional vinyl aromatic copolymer as the polyfunctional vinyl aromatic copolymer (A) in producing the combined rubber.
多官能ビニル芳香族共重合体(A)の末端を構成する構造単位(d)としては、下記(d1)~(d6)で表される単位のいずれかである。ただし、(d4)又は(d5)で表される単位の場合は、(d4)又は(d5)で表される単位を同時に有する。
(式中、R2は炭素数6~30の芳香族炭化水素基を示す。)
(式中、R3は炭素数6~30の芳香族炭化水素基を示し、R4は水素原子又は炭素数6~30の炭化水素基を示す。)The structural unit (d) constituting the terminal of the polyfunctional vinyl aromatic copolymer (A) is any of the units represented by the following (d1) to (d6). However, in the case of the unit represented by (d4) or (d5), the unit represented by (d4) or (d5) is simultaneously held.
(In the formula, R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.)
(In the formula, R 3 indicates an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 4 indicates a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms.)
―Y-O-Z (d3)
(式中、Yは未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示し、Zは炭素数1~30の脂肪族炭化水素基、又は未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示す。)―YOZ (d3)
(In the formula, Y represents an aromatic hydrocarbon group having 6 to 52 carbon atoms substituted with an unsubstituted or hydrocarbon group having 1 to 12 carbon atoms, and Z represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 52 carbon atoms, which is unsubstituted or substituted with a hydrocarbon group having 1 to 12 carbon atoms.)
(ここで、R5は水素原子又は炭素数1~18の炭化水素基を示し、R6及びR7は炭素数1~18の炭化水素基を示し、R8は水素原子又はメチル基を示す。)
(Here, R 5 indicates a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 6 and R 7 indicate a hydrocarbon group having 1 to 18 carbon atoms, and R 8 indicates a hydrogen atom or a methyl group. .)
(ここで、R9は1または2以上の脂環式炭化水素環を有する炭素数4~16の炭化水素基である。)
(Here, R 9 is a hydrocarbon group having 1 or 2 or more alicyclic hydrocarbon rings and having 4 to 16 carbon atoms.)
上記共重合法としては、アニオン重合が適する。 Anionic polymerization is suitable as the above copolymerization method.
また、本発明の他の態様は上記の共重合体ゴムの製造方法で得られた共重合体ゴムに、フィラーを配合し、加硫により架橋させてゴム組成物を得ることを特徴とする架橋ゴム組成物の製造方法である。 Further, another aspect of the present invention is characterized in that a filler is blended with the copolymer rubber obtained by the above-mentioned method for producing a copolymer rubber and crosslinked by vulcanization to obtain a rubber composition. This is a method for producing a rubber composition.
更に、本発明の他の態様は、多官能ビニル芳香族共重合体の構造単位(A1)と、共役ジエン化合物の構造単位(B1)、又は共役ジエン化合物の構造単位(B1)と芳香族ビニル化合物の構造単位(C1)を含有する共重合体ゴムであって、
構造単位(A1)を0.001~6重量%、構造単位(B1)を29~99.999重量%及び構造単位(C1)を0~70重量%含み、
構造単位(A1)が、ジビニル芳香族化合物に由来する構造単位(a)、モノビニル芳香族化合物に由来する構造単位(b)、及び末端を構成する構造単位(d)を含有し、構造単位(a)を2モル%以上95モル%未満含有し、構造単位(a)の少なくとも一部は上記式で表されるビニル基含有構造単位(a1)であり、構造単位(a)の他の少なくとも一部は上記構造単位(d)を構成する構造単位であり、構造単位(a)及び(b)の総和に対するビニル基含有構造単位(a1)モル分率は0.02~0.8の範囲であることを特徴とする共重合体ゴムである。Further, another aspect of the present invention is a structural unit (A1) of a polyfunctional vinyl aromatic copolymer and a structural unit (B1) of a conjugated diene compound, or a structural unit (B1) of a conjugated diene compound and an aromatic vinyl. A copolymer rubber containing a structural unit (C1) of a compound.
It contains 0.001 to 6% by weight of the structural unit (A1), 29 to 99.999% by weight of the structural unit (B1), and 0 to 70% by weight of the structural unit (C1).
The structural unit (A1) contains a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (d) constituting a terminal, and is a structural unit ( It contains 2 mol% or more and less than 95 mol% of a), and at least a part of the structural unit (a) is a vinyl group-containing structural unit (a1) represented by the above formula, and at least the other structural unit (a). Some of them are structural units constituting the structural unit (d), and the molar fraction of the vinyl group-containing structural unit (a1) with respect to the sum of the structural units (a) and (b) is in the range of 0.02 to 0.8. It is a copolymer rubber characterized by being.
上記共重合体ゴムにおける構造単位(A1)の数平均分子量は300~100000であることがよい。そして、上記共重合体ゴムにおける末端を構成する構造単位(d)が、上記(d1)~(d6)で表される単位のいずれかであることがよい。ただし、(d4)又は(d5)で表される単位の場合は、(d4)又は(d5)で表される単位を同時に有する。 The number average molecular weight of the structural unit (A1) in the above-mentioned copolymer rubber is preferably 300 to 100,000. The structural unit (d) constituting the end of the copolymer rubber may be any of the units represented by the above (d1) to (d6). However, in the case of the unit represented by (d4) or (d5), the unit represented by (d4) or (d5) is simultaneously held.
また、本発明の他の態様は、上記の共重合体ゴムと、フィラーを含有し、この共重合体ゴムが架橋構造を有することを特徴とする架橋ゴム組成物である。さらに、上記共重合体ゴムや架橋ゴム組成物に使用することを特徴とする多官能ビニル芳香族共重合体である。 Another aspect of the present invention is a crosslinked rubber composition containing the above-mentioned copolymer rubber and a filler, wherein the copolymer rubber has a crosslinked structure. Further, it is a polyfunctional vinyl aromatic copolymer characterized by being used in the above-mentioned copolymer rubber and crosslinked rubber composition.
本発明の共重合体ゴムは、分岐構造及びフィラーとの相互作用機能を併せ持つ、特定の多官能ビニル芳香族共重合体の構造単位を有することから、加工性及び強度を兼ね備える。更に、ゲル状物質ができにくく、均質となり、成型材料、樹脂の改質剤等に適用できる。
更に、この共重合体ゴムにフィラーを含有し、架橋させた架橋ゴム組成物は、フィラーの分散性に優れることから、機械的強度、耐摩耗性に優れる。Since the copolymer rubber of the present invention has a structural unit of a specific polyfunctional vinyl aromatic copolymer having a branched structure and a function of interacting with a filler, it has both processability and strength. Furthermore, gel-like substances are difficult to form and become homogeneous, and can be applied to molding materials, resin modifiers, and the like.
Further, the crosslinked rubber composition in which the copolymer rubber contains a filler and is crosslinked is excellent in the dispersibility of the filler, and therefore excellent in mechanical strength and wear resistance.
本発明の共重合体ゴムの製造方法では、原料として多官能ビニル芳香族共重合体(A)、共役ジエン化合物(B)と、必要により芳香族ビニル化合物(C)を含む原料を使用し、共重合させる。 In the method for producing a copolymer rubber of the present invention, a raw material containing a polyfunctional vinyl aromatic copolymer (A), a conjugated diene compound (B) and, if necessary, an aromatic vinyl compound (C) is used as a raw material. Copolymerize.
多官能ビニル芳香族共重合体(A)は、ジビニル芳香族化合物とモノビニル芳香族化合物を共重合させることにより得られ、溶剤溶解性を有するものが好ましい。例えば、トルエン、キシレン、テトラヒドロフラン、ジクロロエタン又はクロロホルムに可溶であることがよい。
多官能ビニル芳香族共重合体(A)の数平均分子量Mnは、300~100000であり、好ましくは500~5000である。また、分子量分布Mw/Mnは3~20の範囲が好ましい。The polyfunctional vinyl aromatic copolymer (A) is obtained by copolymerizing a divinyl aromatic compound and a monovinyl aromatic compound, and is preferably solvent-soluble. For example, it may be soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.
The number average molecular weight Mn of the polyfunctional vinyl aromatic copolymer (A) is 300 to 100,000, preferably 500 to 5,000. The molecular weight distribution Mw / Mn is preferably in the range of 3 to 20.
ジビニル芳香族化合物は構造単位(a)を与え、モノビニル芳香族化合物は構造単位(b)を与える。ジビニル芳香族化合物はビニル基を複数有するため架橋し、分岐構造を与えるが、架橋の程度は溶解性を示す程度に制御される。未反応のビニル基を有する構造単位は上記構造単位(a)又は末端を構成する構造単位(d)としての構造単位(d1)等となり、ビニル基を複数有する多官能構造を与える。 The divinyl aromatic compound gives the structural unit (a), and the monovinyl aromatic compound gives the structural unit (b). Since the divinyl aromatic compound has a plurality of vinyl groups, it is crosslinked to give a branched structure, but the degree of crosslinking is controlled to the extent that it exhibits solubility. The structural unit having an unreacted vinyl group becomes the structural unit (a) or the structural unit (d1) as the structural unit (d) constituting the terminal, and gives a polyfunctional structure having a plurality of vinyl groups.
多官能ビニル芳香族共重合体(A)は、上記構造単位(a)を2モル%以上で、95モル%未満含有する。好ましくは5~90モル%、より好ましくは10~90モル%、特に好ましくは、15~85モル%含む。
そして、構造単位(a)の一部は、上記構造単位(a1)として、これを1モル%以上含むことがよく、好ましくは2~80モル%、より好ましくは5~70モル%、更に好ましくは10~60モル%、特に好ましくは15~50モル%である。
更に、構造単位(a)の一部は、末端を構成する構造単位(d)中に、構造単位(d1)として含まれ、その量は一分子当たり0.7個以上、好ましくは1.0個以上、より好ましくは1.5個以上であることがよい。
なお、上記計算において、構造単位(a)は構造単位(a1)と構造単位(d1)を含む。
また、末端の構造単位(d)は一分子当たり平均2.1個以上、好ましくは2.5個以上、より好ましくは3個以上有することがよい。The polyfunctional vinyl aromatic copolymer (A) contains the structural unit (a) in an amount of 2 mol% or more and less than 95 mol%. It preferably contains 5 to 90 mol%, more preferably 10 to 90 mol%, and particularly preferably 15 to 85 mol%.
Then, a part of the structural unit (a) may contain 1 mol% or more of the structural unit (a1), preferably 2 to 80 mol%, more preferably 5 to 70 mol%, still more preferably. Is 10 to 60 mol%, particularly preferably 15 to 50 mol%.
Further, a part of the structural unit (a) is contained as a structural unit (d1) in the structural unit (d) constituting the terminal, and the amount thereof is 0.7 or more per molecule, preferably 1.0. The number is preferably 1.5 or more, more preferably 1.5 or more.
In the above calculation, the structural unit (a) includes the structural unit (a1) and the structural unit (d1).
Further, it is preferable to have an average of 2.1 or more, preferably 2.5 or more, and more preferably 3 or more of the terminal structural units (d) per molecule.
多官能ビニル芳香族共重合体(A)は、構造単位(b)を5モル%以上で、98モル%未満含有する。好ましくは10~95モル%、より好ましくは10~90モル%、特に好ましくは、15~85モル%含む。構造単位(b)の一部は末端の構造単位(d)としてもよい。この構造単位を構造単位(d2)という。 The polyfunctional vinyl aromatic copolymer (A) contains the structural unit (b) in an amount of 5 mol% or more and less than 98 mol%. It preferably contains 10 to 95 mol%, more preferably 10 to 90 mol%, and particularly preferably 15 to 85 mol%. A part of the structural unit (b) may be a terminal structural unit (d). This structural unit is called a structural unit (d2).
ジビニル芳香族化合物に由来する構造単位(a)は、耐熱性や剛性を発現させるための架橋成分としてのビニル基を含み、一方、モノビニル芳香族化合物に由来する構造単位(b)は、硬化反応に関与するビニル基を有しないため、柔軟性や溶解性等を与える。 The structural unit (a) derived from the divinyl aromatic compound contains a vinyl group as a cross-linking component for developing heat resistance and rigidity, while the structural unit (b) derived from the monovinyl aromatic compound is a curing reaction. Since it does not have a vinyl group involved in, it gives flexibility and solubility.
末端の構造単位(d)は、構造単位(a)と構造単位(b)の一部からなっていてもよいし、モノマーとしてジビニル芳香族化合物とモノビニル芳香族化合物以外の他のモノマー類(G)を使用し、これから生じる構造単位の一部又は全部を末端の構造単位(d)としてもよい。この構造単位を構造単位(d3)という。 The terminal structural unit (d) may be composed of a part of the structural unit (a) and the structural unit (b), and the monomers other than the divinyl aromatic compound and the monovinyl aromatic compound (G). ) May be used, and a part or all of the structural unit resulting from this may be used as the terminal structural unit (d). This structural unit is called a structural unit (d3).
多官能ビニル芳香族共重合体(A)は、特許文献5等に記載の方法により得ることができる。例えば、ジビニル芳香族化合物、モノビニル芳香族化合物と必要により他のモノマー類(G)を含むモノマーを、溶媒に溶解させた均一溶媒中、20~120℃の温度で重合させることにより得られる。 The polyfunctional vinyl aromatic copolymer (A) can be obtained by the method described in Patent Document 5 and the like. For example, it can be obtained by polymerizing a monomer containing a divinyl aromatic compound, a monovinyl aromatic compound and, if necessary, another monomer (G) at a temperature of 20 to 120 ° C. in a uniform solvent dissolved in a solvent.
ジビニル芳香族化合物の例としては、ジビニルベンゼン(各異性体含む)、ジビニルナフタレン(各異性体を含む)、ジビニルビフェニル(各異性体を含む)が好ましく使用されるが、これらに限定されるものではない。また、これらは単独又は2種以上を組み合わせて用いることができる。成形加工性の観点から、より好ましくはジビニルベンゼン(m-体、p-体又はこれらの異性体混合物)である。 As examples of the divinyl aromatic compound, divinylbenzene (including each isomer), divinylnaphthalene (including each isomer), and divinylbiphenyl (including each isomer) are preferably used, but are limited thereto. is not. In addition, these can be used alone or in combination of two or more. From the viewpoint of moldability, divinylbenzene (m-form, p-form or a mixture thereof) is more preferable.
モノビニル芳香族化合物の例としては、スチレン、ビニルナフタレン、ビニルビフェニルなどのビニル芳香族化合物、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、o,p-ジメチルスチレン、o-エチルビニルベンゼン、m-エチルビニルベンゼン、p-エチルビニルベンゼンなどの核アルキル置換ビニル芳香族化合物などが挙げられるが、スチレン、エチルビニルベンゼン(各異性体含む)、エチルビニルビフェニル(各異性体を含む)、及びエチルビニルナフタレン(各異性体を含む)が好ましい。 Examples of monovinyl aromatic compounds include vinyl aromatic compounds such as styrene, vinylnaphthalene and vinylbiphenyl, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene and o-ethylvinylbenzene. , M-Ethylvinylbenzene, p-Ethylvinylbenzene and other nuclear alkyl substituted vinyl aromatic compounds, etc., but styrene, ethylvinylbenzene (including each isomer), ethylvinyl biphenyl (including each isomer), And ethylvinylnaphthalene (including each isomer) are preferable.
また、必要により使用される他のモノマー類(G)としては、ジビニル芳香族化合物、モノビニル芳香族化合物と共重合可能なモノマーや、所望の末端基を与える末端変性剤や連鎖移動剤等が挙げられる。 Examples of other monomers (G) used as necessary include divinyl aromatic compounds, monomers copolymerizable with monovinyl aromatic compounds, terminal modifiers and chain transfer agents that give desired terminal groups, and the like. Be done.
多官能ビニル芳香族共重合体(A)の末端を構成する構造単位(d)としては、上記式(d1)~(d6)で表される単位が好ましい。ただし、式(d4)又は式(d5)で表される単位の場合は、式(d4)及び式(d5)で表される単位を同時に有する。 As the structural unit (d) constituting the terminal of the polyfunctional vinyl aromatic copolymer (A), the units represented by the above formulas (d1) to (d6) are preferable. However, in the case of the unit represented by the formula (d4) or the formula (d5), the unit represented by the formula (d4) and the formula (d5) is simultaneously possessed.
式(d1)において、R2は炭素数6~30の芳香族炭化水素基を示す。式(d1)は、モノマーとしてのジビニル芳香族化合物から生じることができる。具体的には、ジビニルベンゼン、ジビニルナフタレン、ジビニルアントラセン、ジビニルフェナンスレンン、ジビニルビフェニル、ジビニルトリフェニル等である。好ましくは、多官能ビニル芳香族共重合体(A)のゴム溶液重合における取扱いの容易性、フィラーとの相互作用に優れることから、ジビニルベンゼン、ジビニルナフタレン、ジビニルビフェニルである。
式(d2)において、R3は炭素数6~30の芳香族炭化水素基を示し、R4は水素原子又は炭素数6~30の炭化水素基を示す。式(d2)は、モノマーとしてのモノビニル芳香族化合物から生じることができる。具体的には、ビニルトルエン、エチルビニルベンゼン、n-プロピルスチレン、イソプロピルスチレン、ブチルスチレン、メチルビニルナフタレン、エチルビニルナフタレン、メチルビニルフェナンスレン、エチルビニルフェナンスレン、メチルビニルアントラセン、エチルビニルアントラセン、メチルビニルビフェニル、エチルビニルビフェニル、メチルビニルトリフェニル、エチルビニルトリフェニル等が挙げられる。好ましくは、多官能ビニル芳香族共重合体(A)のゴム溶液重合における取扱いの容易性、フィラーとの相互作用に優れることから、R3はフェニル基、ナフチル基、ビフェニリル基であり、R4は水素原子または炭素数1~10のアルキル基である。具体的には、ビニルトルエン、エチルビニルベンゼン、n-プロピルスチレン、イソプロピルスチレン、n-ブチルスチレン、イソブチルスチレン、sec-ブチルスチレン、t-ブチルスチレン、メチルビニルナフタレン、エチルビニルナフタレン、メチルビニルビフェニル、エチルビニルビフェニル、等が挙げられる。より好ましくは、ビニルトルエン、エチルビニルベンゼン、イソプロピルスチレン、t-ブチルスチレンである。In formula (d1), R 2 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. The formula (d1) can be derived from a divinyl aromatic compound as a monomer. Specifically, it is divinylbenzene, divinylnaphthalene, divinylanthracene, divinylphenanslenne, divinylbiphenyl, divinyltriphenyl and the like. Divinylbenzene, divinylnaphthalene, and divinylbiphenyl are preferable because the polyfunctional vinyl aromatic copolymer (A) is easy to handle in rubber solution polymerization and has excellent interaction with fillers.
In the formula (d2), R 3 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R 4 represents a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. Formula (d2) can be derived from a monovinyl aromatic compound as a monomer. Specifically, vinyl toluene, ethyl vinylbenzene, n-propylstyrene, isopropylstyrene, butylstyrene, methylvinylnaphthalene, ethylvinylnaphthalene, methylvinylphenanthrene, ethylvinylphenanthrene, methylvinylanthracene, ethylvinylanthracene. , Methylvinylbiphenyl, ethylvinylbiphenyl, methylvinyltriphenyl, ethylvinyltriphenyl and the like. Preferably, R 3 is a phenyl group, a naphthyl group, a biphenylyl group, and R 4 because the polyfunctional vinyl aromatic copolymer (A) is easy to handle in rubber solution polymerization and has excellent interaction with a filler. Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specifically, vinyl toluene, ethyl vinylbenzene, n-propylstyrene, isopropylstyrene, n-butylstyrene, isobutylstyrene, sec-butylstyrene, t-butylstyrene, methylvinylnaphthalene, ethylvinylnaphthalene, methylvinylbiphenyl, Ethylvinylbiphenyl, etc. may be mentioned. More preferably, it is vinyltoluene, ethylvinylbenzene, isopropylstyrene, t-butylstyrene.
式(d3)において、Yは未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示し、Zは炭素数1~30の脂肪族炭化水素基、又は未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示す。式(d3)は、モノマー類(G)として使用されるアニソール、エトキシベンゼン、プロポキシベンゼン、ブトキシベンゼン、メトキシナフタレン、メトキシビフェニル、ビフェニルエーテルから生じることができる。好ましくは、多官能ビニル芳香族共重合体(A)のゴム溶液重合における取扱いの容易性、フィラーとの相互作用に優れることから、アニソール、ブトキシベンゼン、メトキシナフタレンである。 In formula (d3), Y represents an aromatic hydrocarbon group having 6 to 52 carbon atoms substituted with an unsubstituted or hydrocarbon group having 1 to 12 carbon atoms, and Z represents an aliphatic hydrocarbon having 1 to 30 carbon atoms. Indicates an aromatic hydrocarbon group having 6 to 52 carbon atoms, which is a group or an unsubstituted or substituted hydrocarbon group having 1 to 12 carbon atoms. The formula (d3) can be derived from anisole, ethoxybenzene, propoxybenzene, butoxybenzene, methoxynaphthalene, methoxybiphenyl, biphenyl ether used as the monomers (G). Anisole, butoxybenzene, and methoxynaphthalene are preferable because the polyfunctional vinyl aromatic copolymer (A) is easy to handle in rubber solution polymerization and has excellent interaction with a filler.
式(d4)、(d5)において、R5は水素原子又は炭素数1~18の炭化水素基を示し、R6及びR7は炭素数1~18の炭化水素基を示し、R6、R7は互いに結合して環を形成して良い。R6、R7が互いに環を形成する場合は、R6、R7の合計の炭素数は2~36となる。また、R8は水素原子又はメチル基を示す。式(d4)、(d5)は、モノマー類(G)として使用される(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸t-ブチル等、(メタ)アクリル酸2-エチルヘキシルの脂肪族(メタ)アクリレートや、(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロキシル、等の脂環を有する(メタ)アクリレートや、(メタ)アクリル酸フェニル、(メタ)アクリル酸ナフチル等の芳香環を有する(メタ)アクリレート等から生じることができる。好ましくは、多官能ビニル芳香族共重合体(A)のゴム溶液重合における取扱いの容易性、フィラーとの相互作用に優れることから、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸sec-ブチル、(メタ)アクリル酸t-ブチルである。In the formulas (d4) and (d5), R 5 indicates a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 6 and R 7 indicate a hydrocarbon group having 1 to 18 carbon atoms, and R 6 and R 7 may be bonded to each other to form a ring. When R 6 and R 7 form a ring with each other, the total number of carbon atoms of R 6 and R 7 is 2 to 36. Further, R 8 represents a hydrogen atom or a methyl group. Formulas (d4) and (d5) are used as monomers (G), methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (. N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, etc., aliphatic (meth) acrylate of 2-ethylhexyl (meth) acrylate , (Meta) acrylate having an alicyclic such as (meth) cyclopentyl acrylate, (meth) cycloxyl acrylate, or (meth) acrylate having an aromatic ring such as phenyl (meth) acrylate, naphthyl (meth) acrylate. And so on. Preferably, since the polyfunctional vinyl aromatic copolymer (A) is easy to handle in rubber solution polymerization and has excellent interaction with a filler, isopropyl (meth) acrylate, isobutyl (meth) acrylate, (meth). ) S-butyl acrylate and t-butyl (meth) acrylate.
式(d6)において、R9は1または2以上の脂環式炭化水素環を有する炭素数4~6の炭化水素基である。R9は隣接する炭素-炭素二重結合を介して分子鎖と結合する。式(d6)は、モノマー類(G)として使用されるシクロペンテン、シクロヘキセン、ノルボルネン、ジシクロペンタ-モノエン等から生じることができる。好ましくは、多官能ビニル芳香族共重合体(A)のゴム溶液重合における取扱いの容易性、フィラーとの相互作用に優れることから、ノルボルネンである。In formula (d6), R 9 is a hydrocarbon group having 1 or 2 or more alicyclic hydrocarbon rings and having 4 to 6 carbon atoms. R 9 binds to the molecular chain via an adjacent carbon-carbon double bond. The formula (d6) can be derived from cyclopentene, cyclohexene, norbornene, dicyclopenta-monoene and the like used as the monomers (G). Norbornene is preferable because it is easy to handle in rubber solution polymerization of the polyfunctional vinyl aromatic copolymer (A) and is excellent in interaction with a filler.
ジビニル芳香族化合物、モノビニル芳香族化合物と必要により他のモノマー類(G)を含むモノマーを共重合させるための触媒としては、酸触媒又はルイス酸触媒が適する。
酸触媒としては、アルキルスルホン酸、トルエンスルホン酸等のスルホン酸触媒等が使用できる。その使用量は、全モノマー成分の合計100モルに対し、0.1~10モルである。An acid catalyst or a Lewis acid catalyst is suitable as a catalyst for copolymerizing a divinyl aromatic compound or a monovinyl aromatic compound and a monomer containing another monomer (G), if necessary.
As the acid catalyst, a sulfonic acid catalyst such as an alkyl sulfonic acid or a toluene sulfonic acid can be used. The amount used is 0.1 to 10 mol with respect to a total of 100 mol of all the monomer components.
ルイス酸触媒としては、金属イオン(酸)と配位子(塩基)からなる化合物であって、電子対を受け取ることのできるものであれば特に制限なく使用できる。ルイス酸触媒の中でも得られる共重合体の耐熱分解性の観点から、金属フッ化物又はその錯体が好ましく、特にB、Al、Ga、In、Si、Ge、Sn、Pb、Sb、Bi、Ti、W、Zn、Fe及びV等の2~6価の金属フッ化物又はその錯体が好ましい。これらの触媒は、単独又は2種以上を組み合わせて用いることができる。得られる共重合体の分子量及び分子量分布の制御及び重合活性の観点から、三フッ化ホウ素のエーテル錯体が最も好ましく使用される。ここで、エーテル錯体のエーテルとしては、ジエチルエーテル、ジメチルエーテル等がある。
ルイス酸触媒は、全モノマー成分の合計100モルに対し、ルイス酸触媒を0.001~100モルの範囲内で使用することがよく、より好ましくは0.01~50モルである。最も好ましくは0.1~10モルである。
また、所望により助触媒として、1種以上のルイス塩基化合物を使用することができる。ルイス塩基化合物の具体例としては、酢酸エチル等のエステル系化合物、メチルメルカプトプロピオン酸等のチオエステル系化合物、メチルエチルケトン等のケトン系化合物、メチルアミン等のアミン系化合物、ジエチルエーテルのエーテル系化合物、ジエチルスルフィド等のチオエーテル系化合物、及びトリプロピルホスフィン、トリブチルホスフィンなどのホスフィン系化合物がある。The Lewis acid catalyst can be used without particular limitation as long as it is a compound composed of a metal ion (acid) and a ligand (base) and can receive an electron pair. Among the Lewis acid catalysts, metal fluorides or complexes thereof are preferable from the viewpoint of thermal decomposition resistance of the obtained copolymer, and in particular, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Ti, A divalent to hexavalent metal fluoride such as W, Zn, Fe and V or a complex thereof is preferable. These catalysts can be used alone or in combination of two or more. From the viewpoint of controlling the molecular weight and molecular weight distribution of the obtained copolymer and the polymerization activity, an ether complex of boron trifluoride is most preferably used. Here, examples of the ether of the ether complex include diethyl ether and dimethyl ether.
As the Lewis acid catalyst, the Lewis acid catalyst is preferably used in the range of 0.001 to 100 mol, more preferably 0.01 to 50 mol, based on 100 mol of the total monomer components. Most preferably 0.1 to 10 mol.
Further, if desired, one or more Lewis base compounds can be used as a co-catalyst. Specific examples of the Lewis basic compound include an ester compound such as ethyl acetate, a thioester compound such as methyl mercaptopropionic acid, a ketone compound such as methyl ethyl ketone, an amine compound such as methyl amine, an ether compound of diethyl ether, and diethyl. There are thioether-based compounds such as sulfide, and phosphine-based compounds such as tripropylphosphine and tributylphosphine.
重合反応は、例えば、上記モノマーと酸触媒又はルイス酸触媒を、誘電率2.0~15.0の有機溶媒に溶解させた均一溶媒中、20~120℃、好ましくは、40~100℃でカチオン共重合させる方法が適する。
有機溶媒としては、重合活性、溶解性のバランスの観点からトルエン、キシレン、n-へキサン、シクロへキサン、メチルシクロへキサン又はエチルシクロへキサンが特に好ましい。The polymerization reaction is carried out, for example, at 20 to 120 ° C., preferably 40 to 100 ° C. in a uniform solvent in which the above-mentioned monomer and an acid catalyst or a Lewis acid catalyst are dissolved in an organic solvent having a dielectric constant of 2.0 to 15.0. A method of cation copolymerization is suitable.
As the organic solvent, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane or ethylcyclohexane is particularly preferable from the viewpoint of the balance between polymerization activity and solubility.
重合反応停止後、多官能ビニル芳香族共重合体を回収する方法は特に限定されず、例えば、加熱濃縮法、スチームストリッピング法、貧溶媒での析出などの通常用いられる方法を用いればよい。 The method for recovering the polyfunctional vinyl aromatic copolymer after the polymerization reaction is stopped is not particularly limited, and for example, a commonly used method such as a heat concentration method, a steam stripping method, or precipitation in a poor solvent may be used.
上記多官能ビニル芳香族共重合体(A)、共役ジエン化合物(B)と、必要により芳香族ビニル化合物(C)を含む原料を共重合させて共重合体ゴムを製造する。芳香族ビニル化合物(C)は使用しない場合は、ブタジエンゴムやイソプレンゴムのようなジエン系ゴムを得ることができ、芳香族ビニル化合物(C)を使用することによりSBRのような共重ゴムを得ることができる。 A copolymer rubber is produced by copolymerizing the polyfunctional vinyl aromatic copolymer (A) and the conjugated diene compound (B) with a raw material containing an aromatic vinyl compound (C), if necessary. When the aromatic vinyl compound (C) is not used, a diene rubber such as butadiene rubber or isoprene rubber can be obtained, and by using the aromatic vinyl compound (C), a covalent rubber such as SBR can be obtained. Obtainable.
共役ジエン化合物(B)又はこれと芳香族ビニル化合物(C)を含む原料を共重合させて共重合体ゴムを製造する方法は、多官能ビニル芳香族共重合体(A)を原料の1つとして使用する他は、特許文献1~4に記載の方法を採用することができる。 A method for producing a copolymer rubber by copolymerizing a conjugated diene compound (B) or a raw material containing the same and an aromatic vinyl compound (C) is one of the raw materials of a polyfunctional vinyl aromatic copolymer (A). In addition to the above, the methods described in Patent Documents 1 to 4 can be adopted.
共役ジエン化合物(B)としては、1,3-ブタジエン、イソプレン、1,3-ペンタジエン、2,3-ジメチル-1,3-ブタジエン、2-フェニル-1,3-ブタジエン、1,3-ヘキサジエンなどを、単独でまたは2種以上を組み合わせて用いることができるが、これらの中では、1,3-ブタジエン、イソプレン、2,3-ジメチル-1,3-ブタジエンが好ましい。 Examples of the conjugated diene compound (B) include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. Etc. can be used alone or in combination of two or more, but among these, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene are preferable.
また、芳香族ビニル化合物としては、スチレン、α-メチルスチレン、1-ビニルナフタレン、3-ビニルトルエン、エチルビニルベンゼン、ジビニルベンゼン、4-シクロヘキシルスチレン、2,4,6-トリメチルスチレン、tert-ブトキシジメチルシリルスチレンおよびイソプロポキシジメチルシリルスチレンなどを、単独でまたは2種以上を組み合わせて用いることができるが、これらの中では、スチレンが好ましい。 Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, and tert-butoxy. Dimethylsilylstyrene, isopropoxydimethylsilylstyrene and the like can be used alone or in combination of two or more, but among these, styrene is preferable.
共役ジエン化合物(B)として、1,3-ブタジエンを使用し、芳香族ビニル化合物としてスチレンを使用する場合は、いわゆるスチレン―ブタジエンゴム(SBR)が得られる。また、芳香族ビニル化合物としてスチレンを使用しない場合で、共役ジエン化合物(B)として、1,3-ブタジエンを使用する場合は、いわゆるブタジエンゴム(BR)が得られる。共役ジエン化合物(B)としてイソプレンを使用し、芳香族ビニル化合物(C)の構造単位がない場合は、イソプレンゴム(IR)となる。中でもスチレン―ブタジエンゴム(SBR)構造を有すると、耐摩耗性、耐熱性、耐老化性に優れ、特に好ましい。 When 1,3-butadiene is used as the conjugated diene compound (B) and styrene is used as the aromatic vinyl compound, so-called styrene-butadiene rubber (SBR) can be obtained. Further, when styrene is not used as the aromatic vinyl compound and 1,3-butadiene is used as the conjugated diene compound (B), so-called butadiene rubber (BR) can be obtained. When isoprene is used as the conjugated diene compound (B) and there is no structural unit of the aromatic vinyl compound (C), it becomes isoprene rubber (IR). Among them, having a styrene-butadiene rubber (SBR) structure is particularly preferable because it has excellent wear resistance, heat resistance, and aging resistance.
これらを含む原料を共重合させて共重合体ゴムを製造する方法は、制限はないが、炭化水素溶媒中でのアニオン重合が好ましい。
例えば、炭化水素溶媒中において、有機アルカリ金属の化合物を開始剤として用いて、多官能ビニル芳香族共重合体、共役ジエン化合物又はこれらと芳香族ビニル化合物をリビングアニオン重合させる方法や、共役ジエン化合物及び芳香族ビニル化合物をリビングアニオン重合させたのち、多官能ビニル芳香族共重合体を加えて反応を行う多段階反応方法がある。また、必要により末端を、官能基を有する重合停止剤で末端変性してもよい。The method for producing a copolymer rubber by copolymerizing a raw material containing these is not limited, but anionic polymerization in a hydrocarbon solvent is preferable.
For example, a method of subjecting a polyfunctional vinyl aromatic copolymer, a conjugated diene compound, or a living anion polymerization of these with an aromatic vinyl compound in a hydrocarbon solvent using an organic alkali metal compound as an initiator, or a conjugated diene compound. There is also a multi-step reaction method in which a polyfunctional vinyl aromatic copolymer is added after the living anionic polymerization of the aromatic vinyl compound and the reaction is carried out. Further, if necessary, the terminal may be terminal-modified with a polymerization terminator having a functional group.
上記の方法に用いられる炭化水素溶媒の具体例としては、プロパン、n-ブタン、イソブタン、n-ペンタン、イソペンタン、n-へキサン、シクロへキサン、プロペン、1-ブテン、イソブテン、トランス-2-ブテン、シス-2-ブテン、1-ペンチン、2-ペンチン、1-ヘキセン、2-ヘキセン、ベンゼン、トルエン、キシレン、エチルベンゼン、ヘプタン、シクロペンタン、メチルシクロペンタン、メチルシクロヘキサン、1-ペンテン、2-ペンテン、シクロヘキセンなどが挙げられる。 Specific examples of the hydrocarbon solvent used in the above method include propane, n-butene, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutane, and trans-2-. Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene, heptane, cyclopentane, methylcyclopentane, methylcyclohexane, 1-pentene, 2- Examples include pentane and cyclohexene.
また、開始剤として用いられる有機アルカリ金属としては、メチルリチウム、エチルリチウム、n-プロピルリチウム、iso-プロピルリチウム、n-ブチルリチウム、sec-ブチルリチウム、tert-オクチルリチウム、n-デシルリチウム、フェニルリチウム、2-ナフチルリチウム、2-ブチル-フェニルリチウム、4-フェニル-ブチルリチウム、シクロヘキシルリチウム、ジイソプロペニルベンゼンとブチルリチウムとの反応生成物等を挙げることができる。 Examples of the organic alkali metal used as an initiator include methyllithium, ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyllithium, and phenyl. Examples thereof include lithium, 2-naphthyllithium, 2-butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, and reaction products of diisopropenylbenzene and butyllithium.
重合における多官能ビニル芳香族共重合体(A)の使用方法としては特に制限はなく、例として共役ジエン化合物(B)及び必要により芳香族ビニル化合物(C)と共存させて重合を開始する方法、(A)と重合開始剤とを反応させたのちに(B)及び必要により芳香族ビニル化合物(C)を添加する方法、共役ジエン化合物(B)及び必要により芳香族ビニル化合物(C)の重合途中に多官能ビニル芳香族共重合体(A)を添加し、ゴム分子に分岐構造を持たせる方法、共役ジエン化合物(B)及び必要により芳香族ビニル化合物(C)の重合終期に多官能ビニル芳香族共重合体(A)を添加し、ゴム分子をカップリングせしめる方法などが挙げられる。 The method of using the polyfunctional vinyl aromatic copolymer (A) in the polymerization is not particularly limited, and for example, a method of starting the polymerization in coexistence with the conjugated diene compound (B) and, if necessary, the aromatic vinyl compound (C). , (A) and the polymerization initiator, followed by (B) and, if necessary, the method of adding the aromatic vinyl compound (C), the conjugated diene compound (B) and, if necessary, the aromatic vinyl compound (C). A method of adding a polyfunctional vinyl aromatic copolymer (A) during the polymerization to give the rubber molecule a branched structure, a conjugated diene compound (B) and, if necessary, a polyfunctional vinyl compound (C) at the end of polymerization. Examples thereof include a method of adding a vinyl aromatic copolymer (A) to couple rubber molecules.
共重合体ゴムの重量平均分子量は、100,000~500,000の範囲とすることがよい。反応はアルカノールを添加するなどして終了させ、脱溶媒して共重合体ゴムを得ることができる。 The weight average molecular weight of the copolymer rubber is preferably in the range of 100,000 to 500,000. The reaction can be terminated by adding alkanol or the like, and the solvent can be removed to obtain a copolymer rubber.
上記多官能ビニル芳香族共重合体(A)、共役ジエン化合物(B)と、芳香族ビニル化合物(C)の使用割合は、下記の範囲とすることが好ましい。
多官能ビニル芳香族共重合体(A)は、0.001~6重量%、好ましくは0.005~3重量%、更に好ましくは0.01~2重量%であり、共役ジエン化合物(B)は、94~99.999重量%であり、芳香族ビニル化合物(C)は、0~70重量%である。
芳香族ビニル化合物(C)を使用する場合は、多官能ビニル芳香族共重合体(A)は、上記と同様の範囲であり、共役ジエン化合物(B)は50~97重量%、好ましくは55~90重量%であり、芳香族ビニル化合物(C)は、2~50重量%、好ましくは5~45重量%である。
より好ましくは、多官能ビニル芳香族共重合体(A)は、0.01~23重量%、更に好ましくは0.1~1重量%である。共役ジエン化合物(B)は50~97重量%、更に好ましくは55~90重量%である。芳香族ビニル化合物(C)2~49重量%、更に好ましくは5~44重量%の範囲とすることが好ましい。The ratio of the polyfunctional vinyl aromatic copolymer (A), the conjugated diene compound (B) and the aromatic vinyl compound (C) is preferably in the following range.
The polyfunctional vinyl aromatic copolymer (A) is 0.001 to 6% by weight, preferably 0.005 to 3% by weight, more preferably 0.01 to 2% by weight, and the conjugated diene compound (B). Is 94 to 99.999% by weight, and the aromatic vinyl compound (C) is 0 to 70% by weight.
When the aromatic vinyl compound (C) is used, the polyfunctional vinyl aromatic copolymer (A) is in the same range as described above, and the conjugated diene compound (B) is 50 to 97% by weight, preferably 55. It is about 90% by weight, and the aromatic vinyl compound (C) is 2 to 50% by weight, preferably 5 to 45% by weight.
More preferably, the polyfunctional vinyl aromatic copolymer (A) is 0.01 to 23% by weight, still more preferably 0.1 to 1% by weight. The conjugated diene compound (B) is 50 to 97% by weight, more preferably 55 to 90% by weight. The aromatic vinyl compound (C) is preferably in the range of 2 to 49% by weight, more preferably 5 to 44% by weight.
本発明の共重合体ゴムにおける多官能ビニル芳香族共重合体の構造単位(A1)、共役ジエン化合物の構造単位(B1)、及び芳香族ビニル化合物の構造単位(C1)の含有割合は、構造単位(A1)を0.001~6重量%、構造単位(B1)を29~99.999重量%及び構造単位(C1)を0~70重量%含む。
ジビニル芳香族化合物に由来する構造単位(a)、モノビニル芳香族化合物に由来する構造単位(b)、及び末端を構成する構造単位(d)を含有し、構造単位(a)を2モル%以上95モル%未満含有し、構造単位(a)の少なくとも一部は下記式で表されるビニル基含有構造単位(a1)であり、
(式中、R1は炭素数6~30の芳香族炭化水素基を示す。)
構造単位(a)の他の少なくとも一部は上記構造単位(d)を構成する構造単位であり、構造単位(a)及び(b)の総和に対するビニル基含有構造単位(a1)モル分率は0.02~0.8の範囲であり、数平均分子量が300~100000である。
好ましい範囲は、上記原料の使用割合と同様な割合となることがよい。The content ratio of the structural unit (A1) of the polyfunctional vinyl aromatic copolymer, the structural unit (B1) of the conjugated diene compound, and the structural unit (C1) of the aromatic vinyl compound in the copolymer rubber of the present invention is the structure. The unit (A1) is 0.001 to 6% by weight, the structural unit (B1) is 29 to 99.999% by weight, and the structural unit (C1) is 0 to 70% by weight.
It contains a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (d) constituting a terminal, and the structural unit (a) is 2 mol% or more. It contains less than 95 mol%, and at least a part of the structural unit (a) is a vinyl group-containing structural unit (a1) represented by the following formula.
(In the formula, R 1 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.)
At least a part of the other structural unit (a) is a structural unit constituting the structural unit (d), and the molar fraction of the vinyl group-containing structural unit (a1) with respect to the sum of the structural units (a) and (b) is It ranges from 0.02 to 0.8 and has a number average molecular weight of 300 to 100,000.
The preferable range may be a ratio similar to the ratio of the raw materials used.
本発明の架橋ゴム組成物は、上記共重合体ゴムに、フィラーや架橋剤を配合して、ゴム組成物とし、このゴム組成物を加硫により架橋させることにより得ることができる。フィラーとしては、カーボンブラック、シリカ等が挙げられる。特にカーボンブラックとの相互作用に優れる。 The crosslinked rubber composition of the present invention can be obtained by blending a filler or a crosslinking agent with the above-mentioned copolymer rubber to prepare a rubber composition, and crosslinking this rubber composition by vulcanization. Examples of the filler include carbon black and silica. Especially excellent in interaction with carbon black.
フィラーとして含有されるカーボンブラックとしては、SRF、GPF、FEF、HAF、ISAF、SAFなどの各グレードのカーボンブラックを用いることができる。これらの中では、優れた耐摩耗性を有するゴム弾性体が得られることから、HAF、ISAF、SAFが好ましい。
シリカとしては、一般的に充填剤として用いられる粒子状のものであればよいが、一次粒子径が50nm以下のものであることが好ましい。このようなシリカの具体例としては、含水ケイ酸、無水ケイ酸、ケイ酸カルシウム、ケイ酸アルミニウムなどが挙げられる。As the carbon black contained as the filler, carbon black of each grade such as SRF, GPF, FEF, HAF, ISAF, and SAF can be used. Among these, HAF, ISAF, and SAF are preferable because a rubber elastic body having excellent wear resistance can be obtained.
The silica may be in the form of particles generally used as a filler, but the primary particle diameter is preferably 50 nm or less. Specific examples of such silica include hydrous silicic acid, anhydrous silicic acid, calcium silicate, aluminum silicate and the like.
フィラーの含有割合は、共重合体ゴムを含む全ゴム成分100重量部に対して10~120質量部であることが好ましく、補強性とそれによる諸物性の改良効果の観点から、55~100重量部であることが更に好ましい。 The content ratio of the filler is preferably 10 to 120 parts by mass with respect to 100 parts by weight of the total rubber component including the copolymer rubber, and 55 to 100 parts by weight from the viewpoint of reinforcing property and the effect of improving various physical properties. It is more preferably a part.
上記ゴム組成物に含有される架橋剤としては、硫黄による架橋、過酸化物による架橋等特に限定されないが、通常、硫黄が用いられる。架橋剤の含有割合は、全ゴム成分100重量部に対して、0.1~5重量部であることが好ましく、更に好ましくは1~3重量部である。 The cross-linking agent contained in the rubber composition is not particularly limited, such as cross-linking with sulfur and cross-linking with peroxide, but sulfur is usually used. The content ratio of the cross-linking agent is preferably 0.1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the total rubber component.
上記ゴム組成物においては、上記成分の他に、必要に応じて、シランカップリング剤、パラフィン系オイル、ナフテン系オイル、アロマ系オイル等のゴム配合油、ワックス、老化防止剤、ステアリン酸(加硫助剤および加工助剤)、酸化亜鉛、加硫促進剤などが含有されていてもよい。 In the above rubber composition, in addition to the above components, if necessary, a silane coupling agent, a paraffin oil, a naphthen oil, a rubber compound oil such as an aroma oil, a wax, an antiaging agent, and stearic acid (addition). It may contain a vulcanization aid and a processing aid), zinc oxide, a vulcanization accelerator and the like.
上記ゴム組成物は、各成分を、例えばプラストミル、バンバリーミキサー、ロール、インターナルミキサーなどの混練機を用いて混練することによって調製することができる。具体的には、上記の各成分のうち、架橋剤および加硫促進剤以外の成分を混練し、その後、得られた混練物に架橋剤および加硫促進剤を添加して更に混練することが好ましい。 The rubber composition can be prepared by kneading each component using, for example, a kneader such as a plast mill, a Banbury mixer, a roll, or an internal mixer. Specifically, among the above-mentioned components, components other than the cross-linking agent and the vulcanization accelerator may be kneaded, and then the cross-linking agent and the vulcanization accelerator may be added to the obtained kneaded product and further kneaded. preferable.
本発明のゴム組成物は、機械的強度および耐摩耗性に優れるので、低燃費タイヤ、大型タイヤ、高性能タイヤなどのタイヤのトレッドや、サイドウォール部材を得るためのゴム組成物として好適である。また、ゴムベルト、ゴムホース、履物用材料等にも好適に使用できる。 Since the rubber composition of the present invention is excellent in mechanical strength and wear resistance, it is suitable as a rubber composition for obtaining a tread of a tire such as a fuel-efficient tire, a large tire, a high-performance tire, or a sidewall member. .. Further, it can be suitably used for rubber belts, rubber hoses, materials for footwear and the like.
本発明の架橋ゴム組成物は、上記のゴム組成物を架橋処理することによって得られる。例えば、タイヤは、上記のゴム組成物をタイヤの形状(具体的には、トレッドの形状)に応じて押し出し加工し、成形し、これを加硫機中で加熱加圧することによって、トレッドを製造し、このトレッドと他の部品を組み立てることにより、目的とするタイヤを製造することができる。 The crosslinked rubber composition of the present invention is obtained by crosslinking the above rubber composition. For example, a tire is manufactured by extruding the above rubber composition according to the shape of the tire (specifically, the shape of the tread), molding the tire, and heating and pressurizing the rubber composition in a vulcanizer. However, by assembling this tread and other parts, the desired tire can be manufactured.
以下、本発明について実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、各例中の部は特に記載がない場合いずれも重量部であり、各物性の評価は以下に示す方法によって行った。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, the parts in each example are all parts by weight, and the evaluation of each physical property was performed by the method shown below.
1)分子量及び分子量分布
分子量及び分子量分布測定は、GPC(東ソー製、HLC-8220GPC)を使用し、溶媒にテトラヒドロフラン(THF)、流量1.0ml/min、カラム温度38℃、単分散ポリスチレンによる検量線を用いて行った。1) Molecular weight and molecular weight distribution For the measurement of molecular weight and molecular weight distribution, GPC (manufactured by Tosoh, HLC-8220GPC) is used, and the solvent is tetrahydrofuran (THF), the flow rate is 1.0 ml / min, the column temperature is 38 ° C., and the calibration curve is monodisperse polystyrene. It was done using a wire.
2)多官能ビニル芳香族共重合体の構造
日本電子製JNM-LA600型核磁気共鳴分光装置を用い、13C-NMR及び1H-NMR分析により決定した。溶媒としてクロロホルム-d1を使用し、テトラメチルシランの共鳴線を内部標準として使用した。2) Structure of polyfunctional vinyl aromatic copolymer It was determined by 13 C-NMR and 1 H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. Chloroform-d 1 was used as the solvent and the resonance line of tetramethylsilane was used as the internal standard.
3)末端基の解析
末端基の算出は、上記のGPC測定より得られる数平均分子量と13C-NMR及び1H-NMR測定とガスクロマトグラフ(GC)分析の結果より得られるモノマー総量に対する末端基を導入するために使用した誘導体量とから、多官能ビニル芳香族共重合体1分子中に含まれる末端基数を算出した。なお、合成例1においては、末端基はジビニル芳香族化合物又はモノビニル芳香族化合物から生じる。末端基の算出は、13C-NMR及び1H-NMR測定結果に加えて、GC分析より得られる共重合体中に導入された各構造単位の総量に関するデータより、末端に導入された特定の構造単位の導入量を算出し、この末端に導入された特定の構造単位の導入量と上記のGPC測定より得られる数平均分子量とから、多官能ビニル芳香族共重合体1分子中に含まれる特定の構造単位の末端基数を算出した。3) Analysis of terminal groups The terminal groups are calculated based on the number average molecular weight obtained from the above GPC measurement and the total amount of monomers obtained from the results of 13 C-NMR and 1 H-NMR measurements and gas chromatograph (GC) analysis. From the amount of the derivative used for introducing the polyfunctional vinyl aromatic copolymer, the number of terminal groups contained in one molecule of the polyfunctional vinyl aromatic copolymer was calculated. In Synthesis Example 1, the terminal group is derived from a divinyl aromatic compound or a monovinyl aromatic compound. The calculation of the terminal group is based on the data on the total amount of each structural unit introduced into the copolymer obtained by GC analysis in addition to the measurement results of 13 C-NMR and 1 H-NMR. The introduction amount of the structural unit is calculated, and it is contained in one molecule of the polyfunctional vinyl aromatic copolymer from the introduction amount of the specific structural unit introduced at the terminal and the number average molecular weight obtained from the above GPC measurement. The number of terminal groups for a particular structural unit was calculated.
4)ムーニー粘度(ML(1+4)100℃ )
JIS K6300‐1に従って、L形ローター、予熱1分、ローター作動時間4分、温度100℃ で求めた。4) Mooney viscosity (ML (1 + 4) 100 ° C.)
It was determined according to JIS K6300-1 with an L-shaped rotor, preheating for 1 minute, a rotor operating time of 4 minutes, and a temperature of 100 ° C.
5)ゲル状物の確認
共重合体ゴムを5倍重量のシクロヘキサンに溶解して溶液をろ過し、フィルター上の残留物の有無を目視確認した。残留物があればゲル状物ありと判定した。5) Confirmation of gel-like substance The copolymer rubber was dissolved in 5 times the weight of cyclohexane, the solution was filtered, and the presence or absence of residue on the filter was visually confirmed. If there was a residue, it was judged that there was a gel-like substance.
6)引張強度
JIS K6251の引張試験法により300%モジュラスを測定し、比較例1で得られた架橋ゴムの測定値を100として、指数化した。指数値が大きいほど引張り強度に優れることを示す。6) Tensile strength 300% modulus was measured by the tensile test method of JIS K6251, and the measured value of the crosslinked rubber obtained in Comparative Example 1 was set as 100 and indexed. The larger the exponential value, the better the tensile strength.
7)耐摩耗性
JIS K6264に準拠したランボーン型摩耗試験機を使用した方法を用い、スリップ率が30%の摩耗量を測定し、比較例1で得られた架橋ゴムの測定値を100として、指数化した。指数値が大きいほど耐摩耗性は良好である。7) Abrasion resistance Using a method using a Ramborn type abrasion tester compliant with JIS K6264, the amount of wear with a slip ratio of 30% was measured, and the measured value of the crosslinked rubber obtained in Comparative Example 1 was set to 100. Indexed. The larger the index value, the better the wear resistance.
合成例1
DVB-810(新日鉄住金化学製、ジビニルベンゼン成分の含有率81.0wt%)320.5mL(ジビニルベンゼン成分1.82モル、エチルビニルベンゼン成分0.43モル)、酢酸n-ブチル 0.28モル(36.9mL)、トルエン 140mLを1.0Lの反応器内に投入し、70℃で40ミリモルのメタンスルホン酸を酢酸n-ブチル 0.12モル(15.7mL)に溶解させた溶液を添加し、6時間反応させた。重合溶液を水酸化カルシウムで停止させた後、活性アルミナをろ過助剤として、ろ過を行った。それから、60℃で減圧脱揮し、可溶性多官能ビニル芳香族共重合体(共重合体X1)22.6gを得た。
得られた共重合体X1のMnは1085、Mwは12400、Mw/Mnは11.4であった。GC分析、GPC測定、FT-IR、13C‐NMR及び1H‐NMR分析により、共重合体Xは、ジビニル芳香族化合物(a)由来の下記ビニル基含有構造単位(a1)及び末端基(d1)、モノビニル芳香族化合物(b)由来の下記末端基(d2)を有することを確認した。Synthesis example 1
DVB-810 (manufactured by Nippon Steel & Sumitomo Metal Corporation, content of divinylbenzene component 81.0 wt%) 320.5 mL (divinylbenzene component 1.82 mol, ethylvinylbenzene component 0.43 mol), n-butyl acetate 0.28 mol (36.9 mL), 140 mL of toluene was placed in a 1.0 L reactor, and a solution of 40 mmol of methanesulfonic acid at 70 ° C. in 0.12 mol (15.7 mL) of n-butyl acetate was added. And reacted for 6 hours. After stopping the polymerization solution with calcium hydroxide, filtration was performed using activated alumina as a filtration aid. Then, it was devolatile under reduced pressure at 60 ° C. to obtain 22.6 g of a soluble polyfunctional vinyl aromatic copolymer (copolymer X1).
The obtained copolymer X1 had Mn of 1085, Mw of 12400, and Mw / Mn of 11.4. By GC analysis, GPC measurement, FT-IR, 13 C-NMR and 1 H-NMR analysis, the copolymer X is the following vinyl group-containing structural unit (a1) and terminal group derived from the divinyl aromatic compound (a). It was confirmed that d1) has the following terminal group (d2) derived from the monovinyl aromatic compound (b).
(*は、共重合体X1の主鎖との結合部分である。)
(* Is a bonding portion of the copolymer X1 with the main chain.)
また、一分子あたりの末端構造単位(d1)の数は7.7であった。また、共重合体X1は、ジビニルベンゼン成分及びエチルビニルベンゼン由来の構造単位を、両者の合計に対し、それぞれ84.0モル%、及び16.0モル%含有していた。また、全構造に対するビニル基含有構造単位(a1)のモル分率は0.39であった。
また、共重合体X1は、トルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。The number of terminal structural units (d1) per molecule was 7.7. Further, the copolymer X1 contained 84.0 mol% and 16.0 mol%, respectively, of the divinylbenzene component and the structural unit derived from ethylvinylbenzene with respect to the total of both. The mole fraction of the vinyl group-containing structural unit (a1) with respect to the entire structure was 0.39.
In addition, the copolymer X1 was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.
合成例2
DVB-810 276.4mL、トルエン 86.2mL、アニソール93.74mLを1.0Lの反応器内に投入し、50℃で10ミリモルのメタンスルホン酸をトルエン2mLに溶解させた溶液を添加し、4時間反応させた他は、合成例1と同様の手法で共重合体X2を得た。
得られた共重合体X2のMnは1000、Mwは18800、Mw/Mnは18.8であった。GC分析、GPC測定、FT-IR、13C‐NMR及び1H‐NMR分析により、共重合体X2は、ジビニル芳香族化合物(a)由来の合成例1と同様な上記ビニル基含有構造単位(a1)、およびアニソール由来の下記末端基(d3)を有することを確認した。Synthesis example 2
DVB-810 276.4 mL, toluene 86.2 mL, and anisole 93.74 mL were placed in a 1.0 L reactor, and a solution of 10 mmol methanesulfonic acid dissolved in 2 mL of toluene at 50 ° C. was added, and 4 Copolymer X2 was obtained in the same manner as in Synthesis Example 1 except for the time reaction.
The obtained copolymer X2 had Mn of 1000, Mw of 18800, and Mw / Mn of 18.8. By GC analysis, GPC measurement, FT-IR, 13C-NMR and 1H-NMR analysis, the copolymer X2 is the same vinyl group-containing structural unit (a1) as in Synthesis Example 1 derived from the divinyl aromatic compound (a). , And the following terminal group (d3) derived from anisole.
(*は、共重合体主鎖との結合部分である。)
(* Is the bonding portion with the copolymer main chain.)
共重合体X2は、全構造に対しジビニルベンゼン成分由来の構造単位(a)を64.0モル%含有し、またアニソール由来の末端構造基(d3)を一分子あたり平均2.0個含有していた。また、全構造に対するビニル基含有構造単位(a1)のモル分率は0.12であった。また、トルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。 The copolymer X2 contains 64.0 mol% of the structural unit (a) derived from the divinylbenzene component with respect to the entire structure, and contains an average of 2.0 terminal structural groups (d3) derived from anisole per molecule. Was. The mole fraction of the vinyl group-containing structural unit (a1) with respect to the entire structure was 0.12. In addition, it was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.
合成例3
DVB-810 300mL、トルエン 177.6mL、メタクリル酸t-ブチル145.6mL、60℃で10ミリモルのメタンスルホン酸をトルエン2mLに溶解させた溶液を添加し、4時間反応させた他は、合成例1と同様の手法で共重合体X3を得た。
得られた共重合体X3のMnは2190、Mwは13600、Mw/Mnは7.2であった。GC分析、GPC測定、FT-IR、13C‐NMR及び1H‐NMR分析により、共重合体X3は、ジビニル芳香族化合物(a)由来の合成例1と同様な上記ビニル基含有構造単位(a1)、並びにメタクリル酸t-ブチル由来の末端基(d4)(R5、R6、R7=CH3)及び末端基 (d5)(R8=CH3)を有することを確認した。Synthesis example 3
DVB-810 300 mL, toluene 177.6 mL, t-butyl methacrylate 145.6 mL, a solution of 10 mmol methanesulfonic acid dissolved in 2 mL of toluene at 60 ° C. was added and reacted for 4 hours. Copolymer X3 was obtained in the same manner as in 1.
The obtained copolymer X3 had Mn of 2190, Mw of 13600, and Mw / Mn of 7.2. By GC analysis, GPC measurement, FT-IR, 13C-NMR and 1H-NMR analysis, the copolymer X3 is the same vinyl group-containing structural unit (a1) as in Synthesis Example 1 derived from the divinyl aromatic compound (a). , And a terminal group (d4) (R 5 , R 6 , R 7 = CH 3 ) and a terminal group (d 5) (R 8 = CH 3 ) derived from t-butyl methacrylate.
共重合体X3は、全構造に対しジビニルベンゼン成分由来の構造単位(a)を71モル%、メタクリル酸t-ブチル由来の末端構造基(d4)(d5)を一分子あたり平均でそれぞれ1.7個含有していた。また、全構造に対するビニル基含有構造単位(a1)のモル分率は0.53であった。
また、共重合体X3は、トルエン、キシレン、THF、ジクロロエタン、ジクロロメタン、クロロホルムに可溶であり、ゲルの生成は認められなかった。The copolymer X3 contains 71 mol% of the structural unit (a) derived from the divinylbenzene component and the terminal structural groups (d4) and (d5) derived from t-butyl methacrylate on average for the entire structure. It contained 7 pieces. The mole fraction of the vinyl group-containing structural unit (a1) with respect to the entire structure was 0.53.
In addition, the copolymer X3 was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed.
実施例1
窒素置換された内容積0.5リットルのオートクレーブ反応器に、シクロヘキサン245g、THF2.5g、スチレン10g、1,3-ブタジエン40g、合成例1で得られた共重合体X1 0.015gを加えた。25℃において、sec-ブチルリチウム50mgを含むシクロヘキサン溶液5gを添加して重合を開始した。重合熱により反応溶液の温度が上昇し、最高温度は85℃に達した。
重合転化率が99%に達したのを確認後、イソプロパノールを50mg添加して重合停止し、反応溶液に、2,6-ジ-tert-ブチル-p-クレゾール(BHT)を添加した。次いで、スチームストリッピングにより脱溶媒を行い、共重合体ゴムAを得た。得られた共重合体ゴムAの物性を表1に示す。Example 1
245 g of cyclohexane, 2.5 g of THF, 10 g of styrene, 40 g of 1,3-butadiene, and 0.015 g of the copolymer obtained in Synthesis Example 1 were added to an autoclave reactor having an internal volume of 0.5 liters substituted with nitrogen. .. At 25 ° C., 5 g of a cyclohexane solution containing 50 mg of sec-butyllithium was added to initiate polymerization. The temperature of the reaction solution increased due to the heat of polymerization, and the maximum temperature reached 85 ° C.
After confirming that the polymerization conversion rate reached 99%, 50 mg of isopropanol was added to terminate the polymerization, and 2,6-di-tert-butyl-p-cresol (BHT) was added to the reaction solution. Then, the solvent was removed by steam stripping to obtain a copolymer rubber A. Table 1 shows the physical characteristics of the obtained copolymer rubber A.
実施例2
共重合体ゴムA、プロセスオイル、カーボンブラック、酸化亜鉛、ステアリン酸及び老化防止剤を、ラボプラストミルを用い、155℃、60rpmで4分間混練した。
上記混練で得られた混練物に、硫黄と加硫促進剤を加え、ラボプラストミルを用い、70℃、60rpmで1分間混練し、加硫して架橋ゴムAを得た。
各添加物の配合割合を表2に示す。また、架橋ゴムAの物性を表3に示す。Example 2
The copolymer rubber A, process oil, carbon black, zinc oxide, stearic acid and an antiaging agent were kneaded at 155 ° C. and 60 rpm for 4 minutes using a laboplast mill.
Sulfur and a vulcanization accelerator were added to the kneaded product obtained by the above kneading, and the mixture was kneaded at 70 ° C. and 60 rpm for 1 minute using a laboplast mill, and vulcanized to obtain crosslinked rubber A.
Table 2 shows the mixing ratio of each additive. Table 3 shows the physical characteristics of the crosslinked rubber A.
実施例3~4
共重合体X1の代わりに、共重合体X2、共重合体X3をそれぞれ使用した他は、実施例1と同様の手法で、共重合体ゴムC、共重合体ゴムDを得た。得られた物性を表1に示す。Examples 3-4
The copolymer rubber C and the copolymer rubber D were obtained in the same manner as in Example 1 except that the copolymer X2 and the copolymer X3 were used instead of the copolymer X1. The obtained physical properties are shown in Table 1.
実施例5~6
共重合体ゴムAの代わりに、共重合体ゴムC、共重合体ゴムDをそれぞれ使用した他は、実施例2と同様の手法で、架橋ゴムC、架橋ゴムDを得た。得られた物性を表3に示す。Examples 5-6
Crosslinked rubber C and crosslinked rubber D were obtained in the same manner as in Example 2 except that the copolymer rubber C and the copolymer rubber D were used instead of the copolymer rubber A. The obtained physical properties are shown in Table 3.
比較例1
実施例1において、合成例1にて合成した共重合体X1の代わりにDVB-810を、ジビニルベンゼン換算にて0.005g使用した以外は、実施例1と同様の手法で共重合体ゴムBを得た。得られた共重合体ゴムBの物性を表1に示す。Comparative Example 1
In Example 1, the copolymer rubber B was used in the same manner as in Example 1 except that 0.005 g of DVB-810 was used in place of the copolymer X1 synthesized in Synthesis Example 1 in terms of divinylbenzene. Got Table 1 shows the physical characteristics of the obtained copolymer rubber B.
比較例2
さらに、共重合体ゴムBを用いて、実施例1と同様の手法及び各添加物の配合割合で架橋ゴムBを得た。また、架橋ゴムBの物性を表3に示す。Comparative Example 2
Further, using the copolymer rubber B, the crosslinked rubber B was obtained by the same method as in Example 1 and the blending ratio of each additive. Table 3 shows the physical characteristics of the crosslinked rubber B.
なお、表2において、使用した添加剤は、以下のとおり。
ゴム配合油:出光興産製 ダイナプロセスオイル AC-12
硫黄:鶴見化学工業製 粉末硫黄
酸化亜鉛:三井金属鉱業製 亜鉛華1号
ステアリン酸:日油製
カーボンブラック:新日化カーボン製 ニテロン#300
加硫促進剤:N-tert-ブチルベンゾチアゾール-2-スルフェンアミド
老化防止剤:大内新興化学工業製 ノクセラーNS
配合ゴムThe additives used in Table 2 are as follows.
Rubber compound oil: Idemitsu Kosan Dyna Process Oil AC-12
Sulfur: Tsurumi Kagaku Kogyo Co., Ltd. Powdered sulfur Zinc oxide: Mitsui Mining & Smelting Co., Ltd. Zinc Hua No. 1 Stearic acid: Nikko Carbon Black: Shin Nikka Carbon Co., Ltd. Niteron # 300
Vulcanization accelerator: N-tert-butylbenzothiazole-2-sulfenamide Anti-aging agent: Noxeller NS manufactured by Ouchi Shinko Kagaku Kogyo
Blended rubber
表1、表3より、本発明のゴム組成物は公知の分岐剤であるジビニルベンゼンを用いた場合と同等の加工性を与え、かつカーボンブラックを配合した加硫ゴムにおいて、引張強度、耐摩耗性に優れることが分かる。 From Tables 1 and 3, the rubber composition of the present invention provides the same processability as the case of using divinylbenzene, which is a known branching agent, and is a vulcanized rubber containing carbon black, and has tensile strength and abrasion resistance. It turns out that it is excellent in sex.
本発明の共重合体ゴムは、タイヤ(特にタイヤトレッド)、免震用ゴム、ゴムホース、ゴムローラー、履物材料等のエラストマー材料として有用である。
The copolymer rubber of the present invention is useful as an elastomer material for tires (particularly tire treads), seismic isolation rubbers, rubber hoses, rubber rollers, footwear materials and the like.
Claims (7)
多官能ビニル芳香族共重合体(A)の使用割合が、0.001~6重量%であり、
多官能ビニル芳香族共重合体(A)が、ジビニル芳香族化合物に由来する構造単位(a)、モノビニル芳香族化合物に由来する構造単位(b)、及び末端を構成する構造単位(d)を含有し、
末端を構成する構造単位(d)が、下記(d1)~(d6)で表されるいずれかの構造単位(ただし、(d4)又は(d5)で表される単位の場合は、(d4)又は(d5)で表される単位を同時に有する。)、ジビニル芳香族化合物若しくはモノビニル化合物と共重合可能なモノマーに由来する構造単位、又は末端変性剤若しくは連鎖移動剤に由来する構造単位であり、
―Y-O-Z (d3)
(式中、Yは未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示し、Zは炭素数1~30の脂肪族炭化水素基、又は未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示す。)
構造単位(a)を2モル%以上95モル%未満含有し、構造単位(a)の少なくとも一部は下記式で表されるビニル基含有構造単位(a1)であり、
構造単位(a)の他の少なくとも一部は上記構造単位(d)を構成する構造単位であり、構造単位(a)及び(b)の総和に対するビニル基含有構造単位(a1)モル分率は0.02~0.8の範囲であり、数平均分子量が300~100000であり、溶剤可溶性であることを特徴とする共重合体ゴムの製造方法。 In producing a copolymer rubber by copolymerizing a raw material containing a polyfunctional vinyl aromatic copolymer (A) and a conjugated diene compound (B).
The proportion of the polyfunctional vinyl aromatic copolymer (A) used is 0.001 to 6% by weight.
The polyfunctional vinyl aromatic copolymer (A) has a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (d) constituting a terminal. Contains,
When the structural unit (d) constituting the terminal is any of the structural units represented by the following (d1) to (d6) (however, when the unit is represented by (d4) or (d5), (d4). Alternatively, it also has a unit represented by (d5)), a structural unit derived from a monomer copolymerizable with a divinyl aromatic compound or a monovinyl compound, or a structural unit derived from a terminal modifier or a chain transfer agent.
―YOZ (d3)
(In the formula, Y represents an aromatic hydrocarbon group having 6 to 52 carbon atoms substituted with an unsubstituted or hydrocarbon group having 1 to 12 carbon atoms, and Z represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 52 carbon atoms, which is unsubstituted or substituted with a hydrocarbon group having 1 to 12 carbon atoms.)
The structural unit (a) is contained in an amount of 2 mol% or more and less than 95 mol%, and at least a part of the structural unit (a) is a vinyl group-containing structural unit (a1) represented by the following formula.
At least a part of the other structural unit (a) is a structural unit constituting the structural unit (d), and the molar fraction of the vinyl group-containing structural unit (a1) with respect to the sum of the structural units (a) and (b) is A method for producing a copolymer rubber, which is in the range of 0.02 to 0.8, has a number average molecular weight of 300 to 100,000, and is solvent-soluble.
構造単位(A1)を0.001~6重量%、構造単位(B1)を29~99.999重量%及び構造単位(C1)を0~70重量%含み、
構造単位(A1)が、
ジビニル芳香族化合物に由来する構造単位(a)、モノビニル芳香族化合物に由来する構造単位(b)、及び末端を構成する構造単位(d)を含有し、
末端を構成する構造単位(d)が、下記(d1)~(d6)で表されるいずれかの構造単位(ただし、(d4)又は(d5)で表される単位の場合は、(d4)又は(d5)で表される単位を同時に有する。)、ジビニル芳香族化合物若しくはモノビニル化合物と共重合可能なモノマーに由来する構造単位、又は末端変性剤若しくは連鎖移動剤に由来する構造単位であり、
―Y-O-Z (d3)
(式中、Yは未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示し、Zは炭素数1~30の脂肪族炭化水素基、又は未置換又は炭素数1~12の炭化水素基で置換された炭素数6~52の芳香族炭化水素基を示す。)
構造単位(a)を2モル%以上95モル%未満含有し、構造単位(a)の少なくとも一部は下記式で表されるビニル基含有構造単位(a1)であり、
構造単位(a)の他の少なくとも一部は上記構造単位(d)を構成する構造単位であり、構造単位(a)及び(b)の総和に対するビニル基含有構造単位(a1)モル分率は0.02~0.8の範囲であり、数平均分子量が300~100000であることを特徴とする共重合体ゴム。 A co-containing a structural unit (A1) of a polyfunctional vinyl aromatic copolymer, a structural unit (B1) of a conjugated diene compound, a structural unit (B1) of a conjugated diene compound, and a structural unit (C1) of an aromatic vinyl compound. It ’s a polymer rubber,
It contains 0.001 to 6% by weight of the structural unit (A1), 29 to 99.999% by weight of the structural unit (B1), and 0 to 70% by weight of the structural unit (C1).
The structural unit (A1) is
It contains a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (d) constituting a terminal.
When the structural unit (d) constituting the terminal is any of the structural units represented by the following (d1) to (d6) (however, when the unit is represented by (d4) or (d5), (d4). Alternatively, it also has a unit represented by (d5)), a structural unit derived from a monomer copolymerizable with a divinyl aromatic compound or a monovinyl compound, or a structural unit derived from a terminal modifier or a chain transfer agent.
―YOZ (d3)
(In the formula, Y represents an aromatic hydrocarbon group having 6 to 52 carbon atoms substituted with an unsubstituted or hydrocarbon group having 1 to 12 carbon atoms, and Z represents an aliphatic hydrocarbon group having 1 to 30 carbon atoms. Alternatively, it indicates an aromatic hydrocarbon group having 6 to 52 carbon atoms, which is unsubstituted or substituted with a hydrocarbon group having 1 to 12 carbon atoms.)
The structural unit (a) is contained in an amount of 2 mol% or more and less than 95 mol%, and at least a part of the structural unit (a) is a vinyl group-containing structural unit (a1) represented by the following formula.
At least a part of the other structural unit (a) is a structural unit constituting the structural unit (d), and the molar fraction of the vinyl group-containing structural unit (a1) with respect to the sum of the structural units (a) and (b) is A copolymer rubber having a number average molecular weight in the range of 0.02 to 0.8 and having a number average molecular weight of 300 to 100,000.
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CN109906238A (en) | 2019-06-18 |
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KR20190077408A (en) | 2019-07-03 |
EP3536723B1 (en) | 2023-01-25 |
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WO2018084128A1 (en) | 2018-05-11 |
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